US4408079A - Preparation of alpha-alkylacroleins - Google Patents

Preparation of alpha-alkylacroleins Download PDF

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US4408079A
US4408079A US06/339,505 US33950582A US4408079A US 4408079 A US4408079 A US 4408079A US 33950582 A US33950582 A US 33950582A US 4408079 A US4408079 A US 4408079A
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formaldehyde
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Franz Merger
Hans-Juergen Foerster
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/75—Reactions with formaldehyde

Definitions

  • the present invention relates to a process for the preparation of ⁇ -alkylacroleins by reacting an alkanal with formaldehyde and a secondary amine in the presence of a carboxylic, dicarboxylic or polycarboxylic acid in certain molar ratios within a pH range of from 2.5 to 7 and at from 0° to 150° C.
  • ⁇ -alkylacroleins can be prepared by Mannich condensation of an n-alkanal and formaldehyde with the aid of a secondary amine: ##STR1##
  • the reaction is generally carried out at above 40° C., under pressures of from 1 to 10 bar and at pH ⁇ 3.
  • the alkanal undergoes condensation with formaldehyde in (R 2 ) 2 NH to give the Mannich base, splitting of which gives the ⁇ -alkylacrolein and liberates the amine, which advantageously frequently forms a salt, with a strong acid (HCl, HBr, H 2 SO 4 , H 3 PO 4 or a sulfonic acid), which catalyzes the reaction.
  • Methacrolein and 2-ethylacrolein can thus be prepared from propionaldehyde and n-butyraldehyde, respectively, and formaldehyde by the process disclosed in German Pat. No. 875,194.
  • the process is generally carried out at pH ⁇ 7.
  • Example 1 mentions a yield of 51% of ethylacrolein from n-butyraldehyde and formaldehyde at from 200° to 220° C.
  • U.S. Pat. No. 2,848,499 discloses a similar process for continuous condensation of propionaldehyde/formaldehyde/(R 2 ) 2 NH.HX in a ratio of 1:1:2-5 at from 105° to 120° C. under superatmospheric pressure.
  • the acids mentioned are HCl, H 2 SO 4 , H 3 PO 4 and acetic acid.
  • Example described uses HCl, and indicates that, with a ratio of propionaldehyde:formaldehyde:(CH 3 ) 2 NH.HCl of just 1:1.036:2.5 at 111° C., a conversion of 98.1% of propionaldehyde and a selectivity of 99.6%, based on propionaldehyde, or 99%, based on formaldehyde, are achieved.
  • a large excess of amine salt is used in the process, and this is also uneconomical because of the large amount of material circulating; moreover, if the preferred catalyst dimethylamine hydrochloride is used, the problems described above in respect of working up or disposal also arise here.
  • Russ. Chem. Rev. 33 (1964), 314 discloses the condensation of propionaldehyde, formaldehyde and (C 2 H 5 ) 2 NH.HCl in a ratio of 1.1:1:1 at pH 6-7 and 45° C. for 20 minutes. The liberation of methylacrolein at 45° C. permits production without substantial by-product formation. In contrast, substantial amounts of "polymers" and low yields are said to be obtained at the higher temperature necessary with a catalytic amount, namely 0.1 mole, of (R 2 ) 2 NH/mole of formaldehyde.
  • Relatively cheap low molecular weight amines are preferably used in the last four processes mentioned.
  • simple distillation then gives ⁇ -alkylacroleins, such as methylacrolein or 2-ethylacrolein, with substantial amine contents, so that expensive refining is as a rule indispensable for further processing.
  • Additional amine losses during concentration of the catalyst mixture, after the methylacrolein produced has been isolated, by distilling off the water of reaction and the water introduced with the formaldehyde are greater, the more volatile the amine employed.
  • 2,518,416, 2,639,295 and 2,848,499 are technologically very complicated (large excesses of individual components, and difficult conditions) and/or give poor results; and whilst the Russian process gives good yields in a technically simple manner, it has substantial disadvantages; toxicity problems exclude the use of the recommended catalyst (C 2 H 5 ) 2 NH.HCl; the product is of inferior quality because of the amine content; catalyst consumption is substantial, the disposal of inorganic/organic waste products is difficult and moreover NR 2 H.HCl is highly corrosive.
  • R 1 has the above meaning, with formaldehyde and a secondary amine in the presence of an acid, by a process wherein the reaction is carried out with a molar ratio of starting material II to formaldehyde of 0.9-1.5:1, at a pH of 2.5-7 and at from 0° to 150° C. in the presence of
  • the present invention is based on the observation that a useful process must take into consideration not only the yield but also other results of the reaction, some of which are even more important.
  • all these results are surprising.
  • the process is, particularly, surprisingly, superior to the conventional methods because of its relatively high catalyst efficiency Q.
  • secondary amines in combination with mineral acids, eg. sulfuric acid have Q values of ⁇ 20 moles/equivalent of secondary amine in reactions of n-alkanals with formaldehyde, they give Q values of from 60 to 70 moles/equivalent of secondary amine if they are used together with dicarboxylic or polycarboxylic acids.
  • the alkanal can be reacted with formaldehyde in stoichiometric amount, in less than this amount or in excess, for example in an amount of from 0.9 to 1.5, preferably from 0.95 to 1.2 and especially from 1.0 to 1.10, moles of starting material II per mole of formaldehyde.
  • Preferred starting materials II and accordingly preferred end products I are those where R 1 is alkyl of 1 to 8 carbon atoms.
  • the above radicals can also be substituted by groups which are inert under the reaction conditions, eg. alkoxy or alkyl of 1 to 4 carbon atoms.
  • starting materials II are thus propanal, n-butanal, 3-methylbutanal, n-pentanal, 3-methylhexanal, 3-ethylpentanal, 4-methylhexanal, n-heptanal, n-nonanal and n-decanal.
  • the formaldehyde is advantageously used in aqueous solution, preferably in 20-60 percent strength by weight solution.
  • Aliphatic monocarboxylic, dicarboxylic and polycarboxylic acids of from 2 to 10 carbon atoms are used as the acids.
  • the dicarboxylic acids and polycarboxylic acids (preferably tricarboxylic acids) may also be aromatic or araliphatic carboxylic acids.
  • Dicarboxylic and polycarboxylic acids are more advantageous than monocarboxylic acids.
  • acids examples include acetic acid, propionic acid, methoxyacetic acid, the butyric acids, pentanoic, hexanoic, heptanoic, octanoic, nonanoic and decanoic acid, pivalic acid, 2-ethylbutyric acid, 2-methylpentanoic acid, 2-ethylhexanoic acid and isononanoic acid; pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, pentane-1,3,5-tricarboxylic acid, 3-hydroxyglutaric acid, saccharic acid, ⁇ , ⁇ '-dihydroxyadipic acid and, preferably, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, butane-1,2,4-tricarboxylic acid, 3-ethylpentane-1,3,5-tricar
  • Advantageous amines are those of the formula ##STR4## where R 3 and R 2 can be identical or different and each is alkyl of 1 to 12, advantageously of 1 to 10 and preferably of 1 to 6, carbon atoms, advantageously substituted by one or more hetero-atoms, preferably by hydroxyl and/or secondary or tertiary amino, or R 2 and R 3 , together with the adjacent carbon atom, are members of an advantageously 5-membered or 6-membered ring, which may also contain a nitrogen or oxygen atom.
  • R 2 can also be ##STR5## where R 4 and R 5 can be identical or different and each is alkyl of 2 to 18, advantageously of 2 to 10 and preferably of 2 to 6, carbon atoms which is unsubstituted or substituted by several, advantageously two and preferably one, hydroxyl group, and R 4 can also be H, and x is a number from 2 to 6.
  • the hydroxyl group is advantageously in the ⁇ -position.
  • Secondary amines with a boiling point of not less than 130° C. are preferred.
  • Secondary amines which have a very low volatility such as, for example, the hydroxyalkylamines which can easily be obtained, for example, from ammonia or a primary amine and an alkylene oxide, or amines with two or more amino groups, at least one of which is a secondary amino group, the others being secondary and/or tertiary groups, are particularly preferred.
  • Amines III which can be used therefore include N-methyl-, N-ethyl-, N-propyl-, N-isopropyl-, N-butyl-, N-isobutyl-, N-sec.-butyl-, N-tert.-butyl-, N-pentyl-, N-hexyl-, N-heptyl-, N-octyl-, N-nonyl- and N-decyl-(hydroxyethylamine); corresponding amines which are disubstituted by identical or different substituents chosen from those above; piperidine, morpholine, pyrrolidone, piperazine and N-methylpiperazine; N-ethyl-, N-propyl-, N-isopropyl-, N-butyl-, N-isobutyl-, N-sec.-butyl-, N-tert.-butyl-, N-pentyl-, N-
  • monocarboxylic acids advantageously between 0.05 to 1.5, in particular from 0.06 to 1.4, preferably from 0.3 to 1.25 and especially from 0.6 to 1.1
  • equivalents of amine are used per mole of starting material II.
  • dicarboxylic or polycarboxylic acids advantageously between 0.01 to 1.5, preferably from 0.05 to 1.5 and especially from 0.3 to 1.25, equivalents of dicarboxylic or polycarboxylic acid and advantageously from 0.01 to 1.5, preferably from 0.05 to 1.5 and especially from 0.3 to 1.25
  • equivalents of amine are used per mole of starting material II.
  • the reaction is carried out with an equivalent ratio of carboxylic acid to amine of 1-2:1, preferably 1.05-1.8:1 and especially 1.1-1.5:1.
  • the reaction is carried out at pH 2.5-7, preferably 3-6.5 and especially 3-6, at from 0° C. to 150° C., advantageously from 20° to 130° C., preferably from 30° to 120° C. and especially from 40° to 110° C., and under atmospheric, superatmospheric or reduced pressure, continuously or batchwise.
  • the water content in the starting mixture is advantageously from 20 to 80 percent by weight, preferably from 20 to 40 percent by weight.
  • the reaction can be carried out as follows: a mixture of starting material II, amine III, formaldehyde, water and acid is kept at the reaction temperature for 1-300 minutes, as a rule for 5-120 minutes and preferably for 10-90 minutes. The end product is then isolated from the reaction mixture in a conventional manner, for example by phase separation and/or distillation.
  • the process can be carried out batchwise or continuously in various reactors (eg. stirred kettles, tube reactors).
  • formaldehyde can first be introduced into the catalyst mixture which has been prepared from a secondary amine and a carboxylic acid and has a water content of 30-60 percent by weight, and the starting material II can then be added, or formaldehyde and an alkanal can be run simultaneously, together or in parallel, into the mixture and the mixture can then be allowed to react under the defined conditions.
  • the end product I can be isolated from the mixture by phase separation and/or by batchwise or continuous distillation.
  • the condensation is advantageously carried out in a cascade of 2-3 stirred kettles by simultaneously adding formaldehyde and an alkanal to the circulating catalyst mixture and continuously distilling off from the product mixture, together or in succession, the ⁇ -alkylacrolein and the H 2 O introduced with the formaldehyde and formed during the reaction.
  • a proportion of catalyst mixture corresponding to the consumption of amine III is removed and is worked up or disposed of, for example by residue-free combustion.
  • the ⁇ -alkylacroleins which can be prepared by the process are valuable starting materials for dyes, drugs and pest control agents. Oxidation of the methacroleins gives the corresponding methacrylic acids and from these methacrylates are obtained which are valuable in the production of plastics, acrylic glass, molding materials, profiles, finishes, lubricating oils, adhesives and textile auxiliaries. Regarding the use of the products, reference may be made to the above publications and Ullmanns Encyklopadie der ischen Chemie (4th edition), Volume 16, pages 609 to 614.
  • the amine salt is prepared from 1,125 parts of 40 percent strength by weight oxalic acid (5 moles) and 1,050 parts (10 moles) of diethanolamine. 750 parts of 40 percent strength by weight formaldehyde solution and 580 parts (10 moles) of propionaldehyde are then added at 20° C., and the reaction mixture is kept at from 40° to 50° C. for one hour.
  • the crude end product contains 2.6 percent by weight of water and 0.8 percent by weight of organic impurities. 660 parts (94.3% of theory) of methacrolein of boiling point 68° C./1,013 mbar are obtained by azeotropic distillation.
  • the amine salt is prepared from 2,281 parts of 16 percent strength by weight aqueous adipic acid (2.5 moles) and 215 parts (2.5 moles) of piperazine. 375 parts of 40 percent strength by weight formaldehyde solution and 290 parts (5 moles) of propionaldehyde are then added at 20° C., and the reaction mixture is kept at from 40° to 50° C. for one hour.
  • the crude end product contains 2.5 percent by weight of water and 0.8 percent by weight of organic impurities. 320 parts (91.4% of theory) of methacrolein of boiling point 68° C./1,013 mbar are obtained by distillation.
  • the amine salt is prepared from 1,181 parts of 40 percent strength by weight oxalic acid (5.25 moles) and 1,050 parts (10 moles) of diethanolamine. 750 parts of 40 percent strength by weight formaldehyde solution and 720 parts (10 moles) of n-butyraldehyde are then added at 20° C., and the reaction mixture is kept at from 40° to 50° C. for one hour.
  • the crude end product contains 2.2 percent by weight of water and 1.2 percent by weight of organic impurities. 801 parts (95.4% of theory) of ethylacrolein are obtained by distillation.
  • the amine salt is prepared from 245 parts of 40 percent strength by weight sulfuric acid and 210 parts (2 moles) of diethanolamine. 300 parts of 40 percent strength by weight formaldehyde and 232 parts (4 moles) of propionaldehyde are then added at 20° C., and the reaction mixture is kept at from 40° to 50° C. for 2 hours. Thereafter, the methacrolein is first distilled off, followed by the water introduced with the formaldehyde and that formed during the reaction. A further 300 parts of 40 percent strength by weight formaldehyde and 232 parts of propionaldehyde are added to the catalyst solution thus recovered, and the mixture is left at from 40° to 50° C. for 2 hours.
  • the amine salt is prepared from 225 parts of 40 percent strength by weight oxalic acid and 210 parts (2 moles) of diethanolamine. 300 parts of 40 percent strength by weight formaldehyde and 232 parts (4 moles) of propionaldehyde are then added at 20° C., and the reaction mixture is kept at from 40° to 50° C. for 2 hours. Thereafter, the methacrolein is first distilled off, followed by the water introduced with the formaldehyde and that formed during the reaction. A further 300 parts of 40 percent strength by weight formaldehyde and 232 parts of propionaldehyde are added to the catalyst solution thus recovered, and the mixture is left at from 40° to 50° C. for 2 hours.
  • the amine salt is prepared from 245 parts of 40 percent strength by weight sulfuric acid and 210 parts (2 moles) of diethanolamine. 300 parts of 40 percent strength by weight formaldehyde and 288 parts (4 moles) of n-butyraldehyde are then added at 20° C., and the reaction mixture is kept at from 40° to 50° C. for 2 hours. Thereafter, the 2-ethylacrolein is first distilled off, followed by the water introduced with the formaldehyde and that formed during the reaction. A further 300 parts of 40 percent strength by weight formaldehyde and 288 parts of n-butyraldehyde are added to the catalyst solution thus recovered, and the mixture is left at from 40° to 50° C. for 2 hours.
  • the amine salt is prepared from 1,500 parts of 40 percent strength by weight acetic acid (10 moles) and 1,050 parts (10 moles) of diethanolamine. 750 parts of 40 percent strength by weight formaldehyde solution (10 moles) and 580 parts (10 moles) of propionaldehyde are then added at 20° C., and the reaction mixture is kept at from 40° to 50° C. for one hour.
  • the crude end product contains 2.6 percent by weight of water and 1.8 percent by weight of organic impurities. 643 parts (91.8% of theory) of methacrolein of boiling point 68° C./1,013 mbar are obtained by distillation.
  • the amine salt is prepared from 3,600 parts of 40 percent strength by weight 2-ethylhexanoic acid (10 moles) and 430 parts (5 moles) of piperazine. 750 parts of 40 percent strength by weight formaldehyde solution (10 moles) and 580 parts (10 moles) of propionaldehyde are then added at 20° C., and the reaction mixture is kept at from 40° to 50° C. for one hour.
  • the crude end product contains 2.8% of water and 1.65% of organic impurities. 672 parts (96% of theory) of methacrolein of boiling point 68° C./1,013 mbar are obtained by distillation.
  • the amine salt is prepared from 2,420 parts of 40 percent strength by weight isobutyric acid (1 mole) and 430 parts (5 moles) of piperazine. 750 parts of 40 percent strength by weight formaldehyde solution (10 moles) and 580 parts (10 moles) of propionaldehyde are then added at 20° C., and the reaction mixture is kept at from 40° to 50° C. for one hour.
  • the crude end product contains 2.6% of water and 1.45% of organic impurities. 666 parts (93.7% of theory) of methacrolein of boiling point 68° C./1,013 mbar are obtained by distillation.
  • the amine salt is prepared from 1,850 parts of 40 percent strength by weight propionic acid (10 moles) and 1,290 parts (10 moles) of dibutylamine. 750 parts of 40 percent strength by weight formaldehyde solution (10 moles) and 720 parts (10 moles) of n-butyraldehyde are then added at 20° C., and the reaction mixture is kept at from 40° to 50° C. for one hour.
  • the crude end product contains 2.2 percent by weight of water and 1.2% of organic impurities. 795 parts (94.6% of theory) of ⁇ -ethylacrolein of boiling point 92° C. are obtained by distillation.
  • the amine salt is prepared from 2,900 parts of 40 percent strength by weight 2-methylpentanoic acid (10 moles) and 750 parts (10 moles) of methylhydroxyethylamine 750 parts of 40 percent strength by weight formaldehyde solution (10 moles) and 860 parts (10 moles) of 3-methylbutanal are then added at 20° C., and the reaction mixture is kept at from 40° to 50° C. for 2 hours.
  • the crude end product contains 3.4 percent by weight of water and 2.8 percent by weight of organic impurities. 902 g (92% of theory) of isopropylacrolein of boiling point 108° C. are obtained by distillation.
  • the amine salt is prepared from 1,500 parts of 40 percent strength by weight acetic acid (10 moles) and 430 parts (5 moles) of piperazine. 750 parts of 40 percent strength by weight formaldehyde solution (10 moles) and 1,000 parts (10 moles) of n-hexanal are then added at 20° C., and the reaction mixture is kept at from 40° to 50° C. for 3 hours.
  • the crude end product contains 0.6 percent by weight of water and 2.2 percent by weight of organic impurities. 1,047 parts (93.5% of theory) of n-butylacrolein of boiling point 125° C./1,013 mbar are obtained by distillation.
  • the amine salt is prepared from 1,600 parts of 40 percent strength by weight glutaric acid (B 5 moles) and 1,290 parts (10 moles) of dibutylamine. 750 parts of 40 percent strength by weight formaldehyde solution and 1,000 parts (10 moles) of n-hexanal are then added at 20° C., and the reaction mixture is kept at from 40° to 50° C. for 3 hours.
  • the crude end product contains 0.6 percent by weight of water and 3.1 percent by weight of organic impurities. 1,038 parts (92.7% of theory) of n-butylacrolein of boiling point 125° C./1,013 mbar are obtained by distillation.

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DE3106557A DE3106557A1 (de) 1981-02-21 1981-02-21 Verfahren zur herstellung von (alpha)-alkylacroleinen
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US20110028664A1 (en) * 2001-01-12 2011-02-03 Evonik Stockhausen Gmbh Superabsorbent polymer made from acrylic acid
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JPS57150628A (en) 1982-09-17
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